CN104122246A - Raman-spectrum measuring method for detecting content of melamine in milk products with different matrixes - Google Patents
Raman-spectrum measuring method for detecting content of melamine in milk products with different matrixes Download PDFInfo
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- 229920000877 Melamine resin Polymers 0.000 title claims abstract description 79
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 235000013336 milk Nutrition 0.000 title claims abstract description 42
- 210000004080 milk Anatomy 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 239000008267 milk Substances 0.000 title claims abstract description 37
- 238000001237 Raman spectrum Methods 0.000 title claims abstract description 27
- 235000013365 dairy product Nutrition 0.000 claims abstract description 77
- 238000001069 Raman spectroscopy Methods 0.000 claims abstract description 52
- 239000011159 matrix material Substances 0.000 claims abstract description 26
- 239000012086 standard solution Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 34
- 238000001514 detection method Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 claims description 10
- 239000002086 nanomaterial Substances 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 238000004949 mass spectrometry Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 238000000691 measurement method Methods 0.000 claims description 5
- 239000002070 nanowire Substances 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003623 enhancer Substances 0.000 claims description 4
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 4
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000002082 metal nanoparticle Substances 0.000 claims description 4
- 210000002966 serum Anatomy 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011852 carbon nanoparticle Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 239000012153 distilled water Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 235000011164 potassium chloride Nutrition 0.000 claims description 3
- 239000001103 potassium chloride Substances 0.000 claims description 3
- 239000012744 reinforcing agent Substances 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004611 spectroscopical analysis Methods 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 11
- 238000004458 analytical method Methods 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 description 6
- 235000020185 raw untreated milk Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004445 quantitative analysis Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000007405 data analysis Methods 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001294 liquid chromatography-tandem mass spectrometry Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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Abstract
本发明公开一种用于不同基质乳制品中三聚氰胺含量检测的拉曼光谱测量方法，其包括以下步骤：(a)建立不同基质乳制品的特征曲线的数据库；(b)量取多份某一未知基质的待测乳制品，向其中添加不同浓度的三聚氰胺标准液，得到一系列已知三聚氰胺相对浓度的该基质的乳制品样本；(c)对于所述乳制品样本进行拉曼光谱测试分析并获得相对应的特征峰强，从而获得所述乳制品样本的特征峰强随三聚氰胺相对浓度变化的特征曲线的斜率；(d)利用所述乳制品样本的特征曲线的斜率在步骤(a)中建立的数据库中搜索以找到与之相匹配的特征曲线；(e)利用该特征曲线和待测乳制品的特征峰强计算该待测乳制品中的三聚氰胺的浓度。
The invention discloses a Raman spectrometry method for detecting the content of melamine in dairy products with different bases, which comprises the following steps: (a) establishing a database of characteristic curves of dairy products with different bases; The milk product to be tested of the unknown matrix, to which melamine standard solutions of different concentrations are added to obtain a series of dairy product samples of the matrix with known relative concentrations of melamine; (c) Raman spectrum test analysis is carried out for the dairy product sample and Obtain the corresponding characteristic peak intensity, thereby obtain the slope of the characteristic curve of the characteristic peak intensity of the dairy product sample changing with the relative concentration of melamine; (d) utilize the slope of the characteristic curve of the dairy product sample in step (a) Search in the established database to find a matching characteristic curve; (e) calculate the concentration of melamine in the dairy product to be tested by using the characteristic curve and the characteristic peak intensity of the dairy product to be tested.
Description
技术领域technical field
本发明涉及乳制品中的三聚氰胺含量检测领域，尤其涉及不同基质乳制品中的三聚氰胺含量的检测方法。The invention relates to the field of detection of melamine content in dairy products, in particular to a detection method for the content of melamine in dairy products with different bases.
背景技术Background technique
国家发布了《原料乳与乳制品中三聚氰胺检测方法》(GB/T22388-2008)，规定了原料乳、乳制品以及含乳制品中三聚氰胺的三种测定方法，即高效液相色谱法(HPLC)、液相色谱-质谱/质谱法(LC-MS/MS)和气相色谱-质谱联用法[包括气相色谱-质谱法(GC-MS)，气相色谱-质谱/质谱法(GC-MS/MS)]。虽然这些方法可以进行准确的定性及定量分析，但由于操作复杂、操作条件苛刻、耗材成本高、测试速度慢等限制，使得这些方法只能在实验室进行检测。The state issued the "Measurement Method for Melamine in Raw Milk and Dairy Products" (GB/T22388-2008), which stipulated three methods for the determination of melamine in raw milk, dairy products and dairy products, namely high performance liquid chromatography (HPLC) , liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) and gas chromatography-mass spectrometry [including gas chromatography-mass spectrometry (GC-MS), gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS) ]. Although these methods can perform accurate qualitative and quantitative analysis, due to limitations such as complex operations, harsh operating conditions, high cost of consumables, and slow testing speed, these methods can only be tested in laboratories.
中国检验检疫科学研究院公开了专利申请公开号为CN101477051，题目为《用于液态奶中三聚氰胺现场快速检测的拉曼光谱法及试剂盒》，该专利申请公开了一种采用拉曼光谱法定量检测液态奶中三聚氰胺含量的方法，该方法主要通过研究生鲜奶的拉曼光谱特征峰强随三聚氰胺浓度变化的特征曲线，并利用特征曲线和待测生鲜奶的拉曼光谱。它能够比较快速实现对三聚氰胺的检测，对生鲜奶中三聚氰胺的含量有比较好的检测效果。但对其它液态奶进行检测时，由于各种不同液态奶中成分不同，它们的特征曲线会和生鲜奶有一定差异，而如果仍然按照生鲜奶的特征曲线进行定量计算，会导致计算结果和实际值会有比较大的差异。实际测量结果表明该方法对市售的各种液态奶检测时有比较大的测量偏差。产生测量偏差主要是由于各种不同液态奶中成分不同，而这些不同的基质会对拉曼光谱检测带来很大的影响。因此，解决乳制品中不同基质对测量的干扰是应用拉曼光谱对乳制品中三聚氰胺定量检测面临的主要困难。The Chinese Academy of Inspection and Quarantine has published a patent application publication number of CN101477051, titled "Raman spectroscopy and kit for on-site rapid detection of melamine in liquid milk". The method for detecting the content of melamine in liquid milk mainly adopts the characteristic curve of the characteristic peak intensity of the Raman spectrum of fresh milk changing with the concentration of melamine, and utilizes the characteristic curve and the Raman spectrum of the raw fresh milk to be tested. It can realize the detection of melamine relatively quickly, and has a relatively good detection effect on the content of melamine in raw milk. However, when testing other liquid milks, due to the different components in various liquid milks, their characteristic curves will be different from those of raw milk, and if the quantitative calculation is still performed according to the characteristic curves of raw milk, the calculation results will be There will be a big difference with the actual value. The actual measurement results show that this method has a relatively large measurement deviation for the detection of various liquid milks on the market. The measurement deviation is mainly due to the different components in various liquid milks, and these different matrices will have a great impact on the detection of Raman spectroscopy. Therefore, solving the interference of different matrices in dairy products is the main difficulty in the quantitative detection of melamine in dairy products by Raman spectroscopy.
有鉴于此，确有需要提供一种能快速地和/或准确地对不同基质乳制品中的三聚氰胺含量进行定量分析的方法。In view of this, there is a real need to provide a method that can quickly and/or accurately quantify the content of melamine in dairy products with different bases.
发明内容Contents of the invention
本发明的目的旨在解决现有技术中存在的上述问题和缺陷的至少一个方面。The purpose of the present invention is to solve at least one aspect of the above-mentioned problems and deficiencies in the prior art.
鉴于上述分析可知，本发明的目的之一是建立一套利用拉曼光谱解决乳制品中不同基质干扰的测试和数据分析方法，利用拉曼光谱法实现对不同基质乳制品中三聚氰胺的定量检测。In view of the above analysis, it can be seen that one of the purposes of the present invention is to establish a set of testing and data analysis methods that utilize Raman spectroscopy to solve the interference of different substrates in dairy products, and use Raman spectroscopy to achieve quantitative detection of melamine in dairy products with different substrates.
根据本发明的一个方面，提供了一种用于不同基质乳制品中三聚氰胺含量检测的拉曼光谱测量方法，其包括以下步骤：According to one aspect of the present invention, there is provided a kind of Raman spectrometry method for the detection of melamine content in dairy products with different bases, which comprises the following steps:
(a)建立不同基质乳制品的特征曲线的数据库；(a) establishing a database of characteristic curves of dairy products with different bases;
(b)量取多份某一未知基质的待测乳制品，向其中添加不同浓度的三聚氰胺标准液，得到一系列已知三聚氰胺相对浓度的该基质的乳制品样本；(b) Measure a plurality of dairy products of an unknown matrix, add melamine standard solutions of different concentrations therein, and obtain a series of dairy product samples of the matrix with known relative concentrations of melamine;
(c)对于所述乳制品样本进行拉曼光谱测试分析并获得相对应的特征峰强，从而获得所述乳制品样本的特征峰强随三聚氰胺相对浓度变化的特征曲线的斜率；(c) performing Raman spectroscopic analysis on the dairy product sample and obtaining the corresponding characteristic peak intensity, thereby obtaining the slope of the characteristic curve of the characteristic peak intensity of the dairy product sample as a function of the relative concentration of melamine;
(d)利用所述乳制品样本的特征曲线的斜率在步骤(a)中建立的数据库中搜索以找到与之相匹配的特征曲线；(d) using the slope of the characteristic curve of the dairy product sample to search in the database established in step (a) to find a matching characteristic curve;
(e)利用该特征曲线和待测乳制品的特征峰强计算该待测乳制品中的三聚氰胺的浓度。(e) calculating the concentration of melamine in the dairy product to be tested by using the characteristic curve and the characteristic peak intensity of the dairy product to be tested.
进一步地，在步骤(b)中，在添加三聚氰胺标准液到待测乳制品中之后，还将水、有机溶剂或盐加入到所述待测乳制品中，待混合均匀、经离心处理后，取其清液待测。Further, in step (b), after adding the melamine standard solution to the dairy product to be tested, water, organic solvents or salts are also added to the dairy product to be tested, and after uniform mixing and centrifugation, Take its clear solution for testing.
另外，向所述清液中添加纳米材料增强剂，混合均匀后，形成所述待测乳制品的样本。In addition, a nanomaterial enhancer is added to the serum, and after uniform mixing, a sample of the dairy product to be tested is formed.
在另一实施例中，在步骤(c)中，所述获取特征峰强的方法是：In another embodiment, in step (c), the method for obtaining the characteristic peak intensity is:
将获得的乳制品样本的拉曼光谱进行扣背底处理，以获得平坦的拉曼光谱；The Raman spectrum of the obtained dairy product sample is processed to obtain a flat Raman spectrum;
将拉曼光谱中的第一特征峰拉曼频移处的峰面积除以第二特征峰拉曼频移处的特征峰面积，从而获得特征峰强。The characteristic peak intensity is obtained by dividing the peak area at the Raman frequency shift of the first characteristic peak in the Raman spectrum by the characteristic peak area at the Raman frequency shift of the second characteristic peak.
具体地，所述第一特征峰的拉曼频移在707cm-1附近；所述第二特征峰的拉曼频移在935cm-1附近。Specifically, the Raman frequency shift of the first characteristic peak is around 707 cm −1 ; the Raman frequency shift of the second characteristic peak is around 935 cm −1 .
在另一实施例中，在步骤(a)中，通过高效液相色谱法、液相色谱-质谱/质谱法、或气相色谱-质谱联用法来检测一系列具有相同基质的乳制品样本中三聚氰胺的浓度；In another embodiment, in step (a), melamine is detected in a series of dairy product samples having the same matrix by high performance liquid chromatography, liquid chromatography-mass spectrometry/mass spectrometry, or gas chromatography-mass spectrometry concentration;
利用拉曼光谱法获取这些相同基质的乳制品样本的特征峰强，从而建立该基质乳制品的特征峰强随三聚氰胺浓度变化的特征曲线；Utilize Raman spectrometry to obtain the characteristic peak intensity of these dairy product samples of the same matrix, thereby establish the characteristic curve of the characteristic peak intensity of this matrix dairy product changing with the concentration of melamine;
之后，通过检测多种不同基质乳制品的特征曲线，建立不同基质乳制品特征曲线数据库。Afterwards, by detecting the characteristic curves of a variety of dairy products with different bases, a database of the characteristic curves of dairy products with different bases is established.
优选地，水包括去离子水或蒸馏水；有机溶剂包括酒精或丙酮；盐包括氯化钾或氯化钠。Preferably, water includes deionized water or distilled water; organic solvent includes alcohol or acetone; salt includes potassium chloride or sodium chloride.
优选地，所述纳米材料增强剂包括为尺度在1-1000nm范围内的金属纳米材料、金属纳米线、金属纳米团簇、碳纳米管和碳纳米颗粒中任一种或他们的组合。Preferably, the nanomaterial reinforcing agent includes any one or a combination of metal nanomaterials, metal nanowires, metal nanoclusters, carbon nanotubes and carbon nanoparticles with a size in the range of 1-1000 nm.
更优选地，所述金属纳米颗粒材料包括金、银、铜、镁、铝、铁、钴、镍、钯、铂的纳米颗粒材料。More preferably, the metal nanoparticle material includes gold, silver, copper, magnesium, aluminum, iron, cobalt, nickel, palladium, platinum nanoparticle material.
在另一实施例中，在步骤(c)中，所述获取特征曲线斜率的方法是：In another embodiment, in step (c), the method for obtaining the slope of the characteristic curve is:
根据特征峰强随三聚氰胺浓度的变化通过差量法或直线拟合的方法确定特征曲线的斜率。According to the change of characteristic peak intensity with the concentration of melamine, the slope of characteristic curve is determined by difference method or straight line fitting method.
附图说明Description of drawings
本发明的这些和/或其他方面和优点从下面结合附图对优选实施例的描述中将变得明显和容易理解，其中：These and/or other aspects and advantages of the present invention will become apparent and comprehensible from the following description of preferred embodiments in conjunction with the accompanying drawings, in which:
图1是根据本发明实施例的已经建立的不同基质乳制品的特征曲线的数据库的一部分的示意图。Fig. 1 is a schematic diagram of a part of an established database of characteristic curves of dairy products with different bases according to an embodiment of the present invention.
图2a-2c是采用根据本发明实施例的方法测量某一基质的液态奶的三个添加不同浓度的三聚氰胺标准液之后的待测液态奶样本的拉曼光谱图。2a-2c are Raman spectrograms of three liquid milk samples to be tested after adding different concentrations of melamine standard solutions of a certain matrix of liquid milk measured by the method according to an embodiment of the present invention.
图3是在本发明中通过计算所获得的图2a-2c中的待测液态奶样本的特征曲线的示意图。Fig. 3 is a schematic diagram of the characteristic curves of the liquid milk samples to be tested in Figs. 2a-2c obtained by calculation in the present invention.
具体实施方式Detailed ways
下面通过实施例，并结合附图，对本发明的技术方案作进一步具体的说明。在说明书中，相同或相似的附图标号表示相同或相似的部件。下述参照附图对本发明实施方式的说明旨在对本发明的总体发明构思进行解释，而不应当理解为对本发明的一种限制。The technical solutions of the present invention will be further specifically described below through the embodiments and in conjunction with the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of the embodiments of the present invention with reference to the accompanying drawings is intended to explain the general inventive concept of the present invention, and should not be construed as a limitation of the present invention.
本发明的主要构思是：对同一基质的已知三聚氰胺浓度的乳制品进行拉曼光谱测试分析；建立同一基质乳制品的三聚氰胺浓度和对应拉曼光谱特征峰强的特征曲线；研究分析多种不同基质乳制品的三聚氰胺浓度和对应拉曼光谱特征峰强的特征曲线以建立所述特征曲线的数据库；对待测乳制品采用相对法进行拉曼光谱多点测量以确定特征曲线的斜率，结合数据库建立待测乳制品的特征曲线，利用特征曲线计算待测乳制品中三聚氰胺的含量。The main idea of the present invention is: carry out Raman spectrum test analysis to the milk product of known melamine concentration of the same matrix; Establish the characteristic curve of the melamine concentration of the milk product of the same matrix and the characteristic peak intensity corresponding to Raman spectrum; Research and analyze a variety of different The melamine concentration of the base dairy product and the characteristic curve corresponding to the characteristic peak intensity of the Raman spectrum are used to establish a database of the characteristic curve; the relative method is used to measure the multi-point Raman spectrum of the dairy product to be measured to determine the slope of the characteristic curve, and the database is established The characteristic curve of the dairy product to be tested is used to calculate the content of melamine in the dairy product to be tested.
根据本发明的用于不同基质乳制品中三聚氰胺含量检测的拉曼光谱法包括以下步骤：The Raman spectrometry method used for the detection of melamine content in different matrix milk products according to the present invention comprises the following steps:
1)制备已知三聚氰胺浓度的样本：乳制品中三聚氰胺的浓度可以通过国家标准测定方法(高效液相色谱法(HPLC)、液相色谱-质谱/质谱法(LC-MS/MS)和气相色谱-质谱联用法[包括气相色谱-质谱法(GC-MS)，气相色谱-质谱/质谱法(GC-MS/MS)])进行测定，通过向其中添加不同浓度的三聚氰胺标准液，获得一系列已知三聚氰胺浓度的样本；1) Preparation of samples with known melamine concentration: the concentration of melamine in dairy products can be measured by national standard methods (high performance liquid chromatography (HPLC), liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) and gas chromatography -mass spectrometry [including gas chromatography-mass spectrometry (GC-MS), gas chromatography-mass spectrometry/mass spectrometry (GC-MS/MS)]) is measured, by adding different concentrations of melamine standard solution to it, to obtain a series of samples with known melamine concentrations;
2)拉曼光谱测量：取定量样本，向其中添加定量的水、有机溶剂或者盐等化学药品，混匀后离心，取清液待测。将定量清液和纳米材料增强剂混合，利用拉曼光谱仪测量其拉曼光谱；2) Raman spectrum measurement: take a quantitative sample, add a certain amount of water, organic solvent or salt and other chemicals to it, mix well and centrifuge, and take the clear liquid for testing. Mix the quantitative serum and the nanomaterial enhancer, and measure its Raman spectrum with a Raman spectrometer;
3)特征峰强分析：获取拉曼光谱中三聚氰胺某一特征峰拉曼频移处的信号(或峰面积)相对于另一特征峰拉曼频移处的信号(或峰面积)的相对强度，即某一特征峰的特征峰强；3) Characteristic peak intensity analysis: obtain the relative intensity of the signal (or peak area) at the Raman frequency shift of a certain characteristic peak of melamine relative to the signal (or peak area) at the Raman frequency shift of another characteristic peak in the Raman spectrum , that is, the characteristic peak intensity of a certain characteristic peak;
4)建立特征曲线：对相同基质的乳制品，建立特征峰强随三聚氰胺浓度变化的特征曲线；4) Establish a characteristic curve: for dairy products of the same matrix, establish a characteristic curve in which the characteristic peak intensity varies with the concentration of melamine;
5)建立数据库：对不同基质的乳制品分别建立特征曲线以构成相应的数据库(如图1所示，图1中所示出的三聚氰胺浓度的零点或0ppm，表示牛奶样品中实际上不含有三聚氰胺)；5) establish database: establish characteristic curve respectively to the dairy products of different bases to form corresponding database (as shown in Figure 1, the zero point or 0ppm of the melamine concentration shown in Fig. 1 means that actually do not contain melamine in the milk sample );
6)相对测量：取多份待测乳制品或奶制品，向其中分别添加不同浓度的三聚氰胺标准液，得到一系列已知三聚氰胺相对浓度的不同基质的乳制品待测样本，按照步骤2)方法测量各待测样品的拉曼光谱(如图2a-2c所示)，获取特征峰强；6) Relative measurement: take a plurality of dairy products or dairy products to be tested, and add melamine standard solutions of different concentrations to them respectively to obtain a series of dairy product samples to be tested in different substrates with known relative concentrations of melamine, according to step 2) method Measure the Raman spectrum (as shown in Figure 2a-2c) of each sample to be tested to obtain the characteristic peak intensity;
7)定量分析：利用步骤5)建立的数据库和步骤6)相对测量得到的拉曼光谱的特征峰强，建立待测乳制品的特征曲线(参见图3)。结合特征曲线和待测样本拉曼光谱的特征峰强，定量计算出三聚氰胺浓度。7) Quantitative analysis: use the database established in step 5) and the characteristic peak intensity of the Raman spectrum measured in step 6) to establish a characteristic curve of the dairy product to be tested (see Figure 3). Combining the characteristic curve and the characteristic peak intensity of the Raman spectrum of the sample to be tested, the concentration of melamine is quantitatively calculated.
采用上述的相对测试和数据分析方法，可以对乳制品中三聚氰胺含量实现定量检测，当三聚氰胺含量在2.5mg/kg以上时，检测回收率在80％--110％，相对标准偏差小于10％。Using the above-mentioned relative test and data analysis method, the melamine content in dairy products can be quantitatively detected. When the melamine content is above 2.5 mg/kg, the detection recovery rate is 80%-110%, and the relative standard deviation is less than 10%.
在本发明中，建立不同基质乳制品的特征曲线的数据库具体步骤为：通过国家规定的高效液相色谱法、液相色谱-质谱/质谱法、或气相色谱-质谱联用法来检测一系列具有相同基质的乳制品样本中三聚氰胺的浓度；利用拉曼光谱法获取这些相同基质的乳制品样本的特征峰强，从而建立该基质乳制品的特征峰强随三聚氰胺浓度变化的特征曲线；之后，通过检测多种不同基质乳制品的特征曲线，建立不同基质乳制品特征曲线数据库。In the present invention, the specific steps of establishing the database of the characteristic curves of dairy products with different bases are: to detect a series of The concentration of melamine in the dairy product sample of same matrix; Utilize Raman spectrometry to obtain the characteristic peak intensity of these dairy product samples of same matrix, thereby establish the characteristic curve of the characteristic peak intensity of this matrix dairy product changing with melamine concentration; Afterwards, by Detect the characteristic curves of a variety of dairy products with different bases, and establish a database of the characteristic curves of dairy products with different bases.
在本发明中，步骤2)中应用的纳米材料增强剂包括为尺度在1-1000nm范围内的金属纳米颗粒、纳米线以及纳米团簇、碳纳米管、碳纳米颗粒中的任一种或他们的组合。所述金属纳米颗粒、纳米线或纳米团簇包括金、银、铜、镁、铝、铁、钴、镍、钯、铂中任一种或他们的组合的的纳米颗粒或材料、纳米线或纳米簇。In the present invention, the nanomaterial reinforcing agent used in step 2) includes metal nanoparticles, nanowires and nanoclusters, carbon nanotubes, carbon nanoparticles or any of them in the range of 1-1000nm. The combination. The metal nanoparticles, nanowires or nanoclusters include any one of gold, silver, copper, magnesium, aluminum, iron, cobalt, nickel, palladium, platinum or their combination of nanoparticles or materials, nanowires or nanoclusters.
另外，在步骤2)中，水包括去离子水或蒸馏水；有机溶剂包括酒精或丙酮等；盐包括氯化钾或氯化钠等。In addition, in step 2), water includes deionized water or distilled water; organic solvent includes alcohol or acetone, etc.; salt includes potassium chloride or sodium chloride, etc.
在步骤3)中，所述获取特征峰强的方法是：将获得的乳制品样本的拉曼光谱进行扣背底处理，以获得平坦的拉曼光谱；将拉曼光谱中的第一特征峰的拉曼频移处的对应的峰面积除以第二特征峰的拉曼频移处的对应的特征峰面积，从而获得特征峰强。优选地，所述第一特征峰的拉曼频移在707cm-1附近；所述第二特征峰的拉曼频移在935cm-1附近。In step 3), the method for obtaining the characteristic peak intensity is: the Raman spectrum of the obtained dairy product sample is subjected to background processing to obtain a flat Raman spectrum; the first characteristic peak in the Raman spectrum is The corresponding peak area at the Raman frequency shift of the second characteristic peak is divided by the corresponding characteristic peak area at the Raman frequency shift of the second characteristic peak, thereby obtaining the characteristic peak intensity. Preferably, the Raman frequency shift of the first characteristic peak is around 707 cm -1 ; the Raman frequency shift of the second characteristic peak is around 935 cm -1 .
在本发明中，所述获取特征曲线斜率的方法是：根据特征峰强随三聚氰胺浓度的变化通过差量法或直线拟合的方法确定特征曲线的斜率。In the present invention, the method for obtaining the slope of the characteristic curve is: according to the variation of the characteristic peak intensity with the concentration of melamine, the slope of the characteristic curve is determined by a difference method or a straight line fitting method.
同目前国标《原料乳与乳制品中三聚氰胺检测方法》(GB/T22388-2008)中提到的方法相比，采用拉曼光谱法具有样品前处理简单、实验耗材成本低、可进行现场快速检测等优势。相比于已经报道的其它的拉曼光谱法，本发明最大的优势是解决了基质对检测的干扰。本发明的方法不仅仅局限于对某一种乳制品的检测，对市售的二十多种液态乳制品，它都能实现定量检测，测定限为2.5mg/kg，重现性良好(定量分析，RSD≤10％)。Compared with the method mentioned in the current national standard "Measurement Method for Melamine in Raw Milk and Dairy Products" (GB/T22388-2008), Raman spectroscopy has the advantages of simple sample pretreatment, low cost of experimental consumables, and rapid on-site detection and other advantages. Compared with other Raman spectroscopy methods that have been reported, the biggest advantage of the present invention is that it solves the interference of the matrix to the detection. The method of the present invention is not only limited to the detection of a certain dairy product, it can realize quantitative detection for more than 20 kinds of liquid dairy products available on the market, the determination limit is 2.5mg/kg, and the reproducibility is good (quantitative Analysis, RSD≤10%).
实施例Example
步骤1：向多个离心管中分别倒入500μl已知三聚氰胺浓度的液态奶，向其中分别添加50μl不同浓度的三聚氰胺标准液，并向其中添加800μl无水乙醇，涡旋10秒钟后置于离心机中，于14000rpm转速离心12分钟，取上层清液待测。Step 1: Pour 500 μl of liquid milk with known melamine concentration into multiple centrifuge tubes, add 50 μl of melamine standard solution of different concentrations to it, and add 800 μl of absolute ethanol to it, vortex for 10 seconds and place Centrifuge at 14,000 rpm for 12 minutes in a centrifuge, and take the supernatant for testing.
步骤2：向测试瓶中添加430μl银纳米增强剂的溶液(浓度为100毫克/升，银纳米材料或颗粒的尺度在30-150nm的范围之间)和200μl上述的牛奶清液，涡旋混匀。Step 2: Add 430 μl of a solution of silver nano-enhancer (concentration is 100 mg/liter, the scale of silver nanomaterials or particles is between 30-150 nm) and 200 μl of the above-mentioned milk serum to the test bottle, and vortex to mix uniform.
步骤3：用现有技术中的激光光源发射波长为785nm的拉曼光谱仪检测混合液的拉曼光谱，激光功率为450mw，积分时间为1s，连续扫描光谱15次，取平均光谱。Step 3: Use a Raman spectrometer with a laser light source emission wavelength of 785nm in the prior art to detect the Raman spectrum of the mixture. The laser power is 450mw, the integration time is 1s, and the spectrum is scanned continuously for 15 times, and the average spectrum is taken.
步骤4：将特征峰拉曼频移707cm-1的对应峰的峰面积除以特征峰的拉曼频移为935cm-1的对应峰的峰面积，获得707cm-1拉曼频移处特征峰的拉曼信号的相对强度，即特征峰强。Step 4: Divide the peak area of the corresponding peak whose Raman frequency shift of the characteristic peak is 707cm -1 by the peak area of the corresponding peak whose Raman frequency shift of the characteristic peak is 935cm -1 , and obtain the characteristic peak at the Raman frequency shift of 707cm -1 The relative intensity of the Raman signal, that is, the characteristic peak intensity.
步骤5：对于不同含量三聚氰胺的液态奶样品，建立707cm-1附近特征峰的相对强度随三聚氰胺浓度变化的线性关系的特征曲线。Step 5: For liquid milk samples with different contents of melamine, a characteristic curve of the linear relationship between the relative intensity of the characteristic peak around 707 cm −1 and the change of the melamine concentration is established.
步骤6：对不同基质的液态奶分别建立对应的特征曲线，从而建立多个不同基质的液态奶的特征曲线数据库。如图1所示，其示出了6种不同基质的液态奶(例如牛奶1-6)的拉曼特征峰强随三聚氰胺浓度变化的特征曲线。Step 6: Establish corresponding characteristic curves for liquid milk with different matrices, thereby establishing a plurality of characteristic curve databases for liquid milk with different matrices. As shown in FIG. 1 , it shows the characteristic curves of the Raman characteristic peak intensity of six kinds of liquid milks with different matrices (for example, milk 1-6) as a function of the concentration of melamine.
步骤7：取多份待测的某一未知基质的液态奶，向其中添加不同浓度的三聚氰胺标准液，得到一系列已知三聚氰胺相对浓度的所述未知基质液态奶待测样本。Step 7: Take multiple portions of liquid milk with an unknown matrix to be tested, and add melamine standard solutions of different concentrations to it to obtain a series of liquid milk with unknown matrix to be tested with known relative concentrations of melamine.
具体地，在本实施例中，量取三份500μl的待测液态奶，并分别向其中添加50μl的水、15ppm三聚氰胺标准液和35ppm三聚氰胺标准液，以与上述步骤1和2所述的步骤相同的方法制备液态奶待测样本(即将步骤1和2中的已知三聚氰胺浓度的液态奶替换成同样体积的待测液态奶，保持其它参数、条件或处理顺序完全相同)。假设待测液态奶中三聚氰胺浓度为X，三个样本中三聚氰胺浓度可以看作为X，X+1.5ppm，X+3.5ppm。Specifically, in this embodiment, three parts of 500 μl of liquid milk to be tested are measured, and 50 μl of water, 15 ppm melamine standard solution and 35 ppm melamine standard solution are added thereto respectively, to be consistent with the steps described in steps 1 and 2 above. Prepare the liquid milk test sample in the same way (that is, replace the liquid milk with known melamine concentration in steps 1 and 2 with the same volume of liquid milk to be tested, and keep other parameters, conditions or processing sequence exactly the same). Assuming that the concentration of melamine in the liquid milk to be tested is X, the concentration of melamine in the three samples can be regarded as X, X+1.5ppm, and X+3.5ppm.
步骤8：利用所述待测液态奶的特征曲线的斜率在之前建立的数据库中寻找对应的与之匹配的特征曲线。Step 8: Use the slope of the characteristic curve of the liquid milk to be tested to find the corresponding matching characteristic curve in the previously established database.
具体地，按照前面所述的步骤的方法测量各待测样本的拉曼光谱，获取特征峰强，从而获得待测液态奶的特征曲线。其中参考图2a-2c，示出了待测液态奶的拉曼峰强与拉曼频移的拉曼光谱图。Specifically, measure the Raman spectrum of each sample to be tested according to the method described above to obtain the characteristic peak intensity, thereby obtaining the characteristic curve of the liquid milk to be tested. Referring to Figs. 2a-2c, the Raman spectrograms of Raman peak intensity and Raman frequency shift of the liquid milk to be tested are shown.
通过使用步骤3中的相应的方法，测得三个待测液态奶样本的拉曼光谱，如图2a、2b、2c所示。计算得到特征峰强(707cm-1特征峰拉曼频移处拉曼信号的相对强度)分别为：0.691，1.030，1.426，从而得到三聚氰胺浓度和特征峰强的对应关系，如表1：By using the corresponding method in step 3, the Raman spectra of the three liquid milk samples to be tested are measured, as shown in Figures 2a, 2b, and 2c. The calculated characteristic peak intensity (the relative intensity of the Raman signal at the characteristic peak Raman frequency shift of 707cm -1 ) is respectively: 0.691, 1.030, 1.426, thereby obtaining the corresponding relationship between the melamine concentration and the characteristic peak intensity, as shown in Table 1:
表1示出待测液态奶样本的三聚氰胺相对浓度与特征峰强的关系Table 1 shows the relationship between the relative concentration of melamine and the characteristic peak intensity of the liquid milk sample to be tested
利用三聚氰胺相对浓度和特征峰强计算相应的特征曲线的斜率。将X设置为任意某一值，对上述三组数据进行直线拟合(图3是假设X＝0，得到的拟合曲线)，拟合得到斜率为0.21。通过斜率在数据库中查询匹配的特征曲线为Y＝0.21X+0.37。Calculate the slope of the corresponding characteristic curve by using the relative concentration of melamine and the intensity of the characteristic peak. Set X to any certain value, and perform linear fitting on the above three sets of data (Fig. 3 is the fitting curve obtained assuming X=0), and the slope obtained by fitting is 0.21. The matching characteristic curve is queried in the database by the slope as Y=0.21X+0.37.
步骤9：利用特征曲线和待测液态奶的拉曼光谱的特征峰强定量计算待测液态奶中三聚氰胺的浓度。待测液态奶样品特征峰强Y＝0.691，利用特征曲线计算得到待测液态奶样品三聚氰胺浓度为1.53ppm，非常接近它的实际浓度1.50ppm(该实际浓度是通过国家规定的检测方法获得的)。Step 9: Quantitatively calculate the concentration of melamine in the liquid milk to be tested by using the characteristic curve and the characteristic peak intensity of the Raman spectrum of the liquid milk to be tested. The characteristic peak intensity of the liquid milk sample to be tested is Y=0.691, and the melamine concentration of the liquid milk sample to be tested is calculated by using the characteristic curve to be 1.53ppm, which is very close to its actual concentration of 1.50ppm (the actual concentration is obtained by the detection method stipulated by the state) .
对多个样品按照上述方法进行测量，发现三聚氰胺含量小于或等于2.5-5ppm的范围内，回收率在80％--110％之间，相对标准偏差小于10％。对步骤7，同样可以取多份未知基质的已知三聚氰胺相对浓度的样品进行测量，以确定多个未知基质的液态奶乳制品中的三聚氰胺的浓度。A plurality of samples are measured according to the above method, and it is found that the melamine content is less than or equal to 2.5-5ppm, the recovery rate is between 80%-110%, and the relative standard deviation is less than 10%. For step 7, it is also possible to take a plurality of samples with known relative concentration of melamine in unknown matrix for measurement, so as to determine the concentration of melamine in a plurality of liquid milk dairy products with unknown matrix.
虽然本发明总体构思的一些实施例已被显示和说明，本领域普通技术人员将理解，在不背离本总体发明构思的原则和精神的情况下，可对这些实施例做出改变，本发明的范围以权利要求和它们的等同物限定。While certain embodiments of the present general inventive concept have been shown and described, those of ordinary skill in the art will appreciate that changes may be made to these embodiments without departing from the principles and spirit of the present general inventive concept. The scope is defined by the claims and their equivalents.
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| CN104568909A (en) * | 2015-02-10 | 2015-04-29 | 吕志伟 | Method for detecting content of dicyandiamide in milk based on surface enhanced Raman scattering technology |
| CN105628669A (en) * | 2014-10-28 | 2016-06-01 | 河北伊诺光学科技有限公司 | Detection method of melamine in milk and milk powder |
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| CN107247045A (en) * | 2017-06-16 | 2017-10-13 | 王海燕 | The dairy products Raman spectral characteristics extracting method parsed based on chemical prior information |
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| CN108020539A (en) * | 2018-01-17 | 2018-05-11 | 南开大学 | The enhancing Raman optical spectrum method that a kind of food security quickly detects |
| CN109239049A (en) * | 2018-09-13 | 2019-01-18 | 常州常检诺食品检测中心有限公司 | The detection method of melamine in a kind of milk powder |
| CN111380856A (en) * | 2018-12-29 | 2020-07-07 | 同方威视技术股份有限公司 | Method for detecting melamine in dairy product by using Raman spectrum |
| CN114441503A (en) * | 2022-01-21 | 2022-05-06 | 首都师范大学 | Melamine quantitative detection method based on surface enhanced Raman spectrum internal standard analysis |
| CN114441503B (en) * | 2022-01-21 | 2023-07-28 | 首都师范大学 | Melamine quantitative detection method based on surface enhanced Raman spectrum internal standard analysis |
| CN114813592A (en) * | 2022-03-11 | 2022-07-29 | 华南理工大学 | A method to explore the degradation mechanism of hydroxychloroquine in natural water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104122246B (en) | 2017-03-29 |
| US8891081B1 (en) | 2014-11-18 |
| WO2014176869A1 (en) | 2014-11-06 |
| US20140320855A1 (en) | 2014-10-30 |
| HK1200531A1 (en) | 2015-08-07 |
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